Semiconductor device and the method of manufacturing the same

ABSTRACT

A semiconductor device includes a semiconductor substrate; a metal electrode wiring laminate on the semiconductor substrate, the metal electrode wiring laminate being patterned with a predetermined wiring pattern; the metal electrode wiring laminate including an undercoating barrier metal laminate and aluminum or aluminum alloy film on the undercoating barrier metal laminate; and organic passivation film covering the metal electrode wiring laminate, wherein the barrier metal laminate is a three-layered laminate including titanium films sandwiching a titanium nitride film. The semiconductor device according to the invention facilitates improving the moisture resistance of the portion of the barrier metal laminate exposed temporarily in the manufacturing process, facilitates employing only one passivation film, facilitates preventing the failures caused by cracks from occurring and the failures caused by Si nodules remaining in the aluminum alloy from increasing.

CROSS REFERENCE TO RELATED APPLICATION

This is a divisional of Ser. No. 12/243,477, filed Oct. 1, 2008, forwhich benefit is claimed, and status is now U.S. Pat. No. 8,102,050,which in turn claims priority from JP Application No. 2007-258649, filedOct. 2, 2007, the content of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a semiconductor device used insemiconductor integrated circuits and the method for manufacturing thesemiconductor device. Specifically, the invention relates to asemiconductor device that has a multilayered electrode structureincluding a metal electrode wiring laminate formed on a semiconductorsubstrate and having a predetermined wiring pattern. The metal electrodewiring laminate includes an undercoating barrier metal laminate and analuminum film or an aluminum alloy film formed on the undercoatingbarrier metal laminate. The metal electrode wiring laminate is coveredwith a passivation film. Specifically, the invention further relates tothe method for manufacturing the semiconductor device having themultilayered electrode structure described above.

The method for manufacturing the semiconductor device having aconventional multilayered electrode structure will be described belowfocusing especially on the method for forming the conventionalmultilayered electrode structure relevant to the present invention. Theconventional multilayered electrode structure includes a metal electrodewiring laminate including a barrier metal laminate, formed of a Ti filmand a TiN film, and an Al—Si alloy film on the barrier metal laminate.An organic passivation film formed of a polyimide film is coated on themetal electrode wiring laminate.

The manufacturing process flow, along which the manufacture of theconventional multilayered electrode structure, will be described withreference to FIGS. 3( a) through 3(e) and FIGS. 4( f) through 4(i). Inthe following descriptions, titanium, aluminum and silicon will bedesignated sometimes by the respective atomic symbols, Ti, Al and Si.

As described in FIG. 3( a), Ti film 3 and TiN film 4 are formed bysputtering as the constituent films of the barrier metal laminate in theorder of the above descriptions thereof from the side of a siliconsubstrate, in which semiconductor functional regions not shown areformed. An Al—Si alloy film 2 is then laminated on TiN film 4 (step(a)). A photoresist 1 is formed on Al—Si alloy film 2 and photoresist 1is patterned as described in FIG. 3( b) to form a predetermined wiringpattern (step (b)). Then, Al—Si alloy film 2 is etched by wet etchingwith a mixed acid (nitric acid:acetic acid:phosphoric acid=1-10:1-20:10-40 (in the volume ratio)) at a liquid temperature of 40-80° C.using patterned photoresist 1 as a mask. As described in FIG. 3( c),Al—Si alloy film 2 is side-etched to the underside of photoresist 1working as a mask. Si nodules 5 (Si particles and such particle residuescaused by etching Al—Si alloy film 2) shown by open circles in FIG. 3(c) remain on the barrier metal laminate surface, from which Al—Si alloyfilm 2 is removed by the etching. Si nodules 5 are caused also in thealuminum alloy film (step (c)). The Si nodules 5, which remain on thebarrier metal laminate surface, are removed as described in FIG. 3( d)by plasma etching using a fluorine-containing gas as a main etching gas.The plasma etching conditions include the CF₄ gas flow rate of 100 to500 sccm, the O₂ gas flow rate of 5 to 50 sccm, the pressure inside achamber of 66.66 to 199.98 Pa, the plasma electric power of 0.2 to 2.0W/cm², and the wafer temperature of 30 to 90° C. (step (d)). Then, asdescribed in FIG. 3( e), Ti film 3 and TiN film 4 are etched and removedby dry etching with a chlorine-containing gas as a main etching gasusing photoresist 1 for a mask. The dry etching conditions include theBCl₃ gas flow rate of 30 to 80 sccm, the Cl₂ gas flow rate of 30 to 80sccm, the N₂ gas flow rate of 0 to 30 sccm, the pressure inside achamber of 19.99 to 39.99 Pa, the plasma electric power of 400 to 1000W/cm², the cathode electrode temperature of 50 to 100° C., and the wallelectrode temperature of 50 to 100° C. As described above, Al—Si alloyfilm 2 is set back from the pattern edge of photoresist 1. However, Tifilm 3 and TiN film 4 are etched such that Ti film 3 and TiN film 4 arepatterned with the pattern of photoresist 1. Therefore, the surface ofTiN film 4, which is the uppermost constituent film of the barrier metallaminate, is exposed in the area, from which Al—Si alloy film 2 has beenetched and removed (step (e)).

The photoresist 1 is then burned to ashes and removed as described inFIG. 4( f) (step (f)). Then, a heat treatment is conducted to sinter Tifilm 3, TiN film 4 and Al—Si alloy film 2. As Ti film 3, TiN film 4 andAl—Si alloy film 2 are sintered, Si nodules 5 in the aluminum alloy growas described in FIG. 4( g). The growth of Si nodules 5 is illustrated bylarger open circles in FIG. 4( g). Si nodules 5 grow to be larger as theheat treatment temperature is higher and as the heat treatment time islonger (step (g)). Then, SiN film 8 is coated to protect exposed Ti film3 and TiN film 4 from moistures as described in FIG. 4( h) (step (h)).The polyimide film 7 is then coated to protect the semiconductor devicesurface as described in FIG. 4( i) (step (i)).

Manufacturing steps, almost identical to the steps (a) through (g) forforming the multilayered electrode structure described above, aredescribed in the following Unexamined Laid Open Japanese PatentApplication Publication No. 2004-79582. The semiconductor device, havinga multilayered electrode structure that includes an Al—Si alloy film ona barrier metal laminate formed of a Ti film, a TiON film on the Tifilm, and a Ti-film on the TiON film, is disclosed in the followingUnexamined Laid Open Japanese Patent Application Publication No.2001-68473.

In the manufacturing process described above in the section ofbackground and in the manufacturing process described in Publication No.2004-79582, the barrier metal laminate surface is exposed widely. Asshown in FIGS. 3( e), 4(f) and 4(g), a widely exposed area is caused inthe barrier metal laminate surface due to the removal of Al—Si film 2therefrom by the wet etching. When the barrier metal laminate exhibitspoor moisture resistance, it is necessary to protect the exposed surfacearea of the barrier metal laminate with a passivation film such as asilicon nitride film (hereinafter referred to as a “SiN film”) thatexhibits excellent moisture resistance. Although the SiN film exhibitsexcellent moisture resistance, defects such as cracks are liable to becaused in the SiN film by the surface stress due to the thermalexpansion coefficient difference between the SiN film and the siliconsubstrate. For a countermeasure against the detect formation, it isnecessary to further laminate an organic passivation film such as apolyimide film on the SiN film. As a result, it is necessary for theconventional manufacturing processes to form two passivation films. Theformation of two passivation films makes the manufacturing costs soarinevitably. A large stress is exerted to the SiN film surface asdescribed above. When the SiN film is combined a thin silicon wafer, alarge warp is caused in the thin silicon wafer. It is impossible to makethe warped silicon wafer flow through the subsequent manufacturingsteps. The Si nodules caused in the Al—Si alloy film grow to be largeras the heat treatment temperature is higher when the TiN film is on thesurface side in the barrier metal laminate. The large Si nodules causestart points in the SiN film, from which cracks are caused in the wirebonding step in the assembly process, further causing failure increase.

In view of the foregoing, it would be desirable to provide a device andmethod that obviates the problems described above. It would further bedesirable to provide a semiconductor device, including a metal electrodewiring laminate, which facilitates improving the moisture resistance ofthe exposed portion of the barrier metal laminate including a TiN filmon the surface side therein. It would also be desirable to provide asemiconductor device, including a metal electrode wiring laminate andone passivation film protecting the metal electrode wiring laminate,which facilitates preventing the cracks due to the Si nodule growth fromcausing in the aluminum alloy film. It would still further be desirableto provide the method of manufacturing a semiconductor device, includinga metal electrode wiring laminate, that facilitates preventing thefailures caused by the cracks due to the Si nodule growth fromincreasing.

SUMMARY OF THE INVENTION

The invention provides a device and method that obviates the problemsdescribed above. Specifically, the invention provides a semiconductordevice, including a metal electrode wiring laminate, which facilitatesimproving the moisture resistance of the exposed portion of the barriermetal laminate including a TiN film on the surface side therein.Further, the invention provides a semiconductor device, including ametal electrode wiring laminate and one passivation film protecting themetal electrode wiring laminate, which facilitates preventing the cracksdue to the Si nodule growth from causing in the aluminum alloy film.Still further, the invention provides a method of manufacturing asemiconductor device, including a metal electrode wiring laminate, thatfacilitates preventing the failures caused by the cracks due to the Sinodule growth from increasing.

In one preferred embodiment, a semiconductor device includes asemiconductor substrate, a metal electrode wiring laminate including anundercoating barrier metal laminate and an aluminum film or an aluminumalloy film on the barrier metal laminate, the metal electrode wiringlaminate being patterned with a predetermined wiring pattern, an organicpassivation film covering the metal electrode wiring laminate, and thebarrier metal laminate including titanium films and a titanium nitridefilm between the titanium films.

The uppermost one of the titanium films is preferably from 20 nm to 100nm in thickness, the aluminum film or the aluminum alloy film ispreferably 3 μm or more in thickness, the organic passivation film ispreferably a polyimide film in the semiconductor device, thesemiconductor substrate is preferably a silicon semiconductor substrate,and the aluminum alloy film is preferably an aluminum-silicon alloyfilm.

In another preferred embodiment, a method of manufacturing asemiconductor device is provided that includes forming a barrier metallaminate on a semiconductor substrate, the barrier metal laminateincluding titanium films and a titanium nitride film between thetitanium films, forming an aluminum film or an aluminum alloy film onthe uppermost one of the titanium films in the barrier metal laminate,etching the aluminum film or the aluminum alloy film by wet etchingusing a mixed acid for patterning the aluminum film or the aluminumalloy film with a predetermined wiring pattern, etching the residueremaining on the exposed surface of the barrier metal laminate by plasmaetching using a mixed gas containing a fluorine-containing gas forremoving the residue, etching the barrier metal laminate by plasmaetching using a mixed gas containing a chlorine-containing gas forpatterning the barrier metal laminate with the predetermined wiringpattern, and coating an organic passivation film.

The mixed acid preferably contains nitric acid and acetic acid or themixed acid preferably contains nitric acid, acetic acid, and phosphoricacid, the uppermost one of the titanium films is preferably from 20 nmto 100 nm in thickness, the aluminum film or the aluminum alloy film ispreferably 3 μm or more in thickness, the semiconductor substrate ispreferably a silicon semiconductor substrate, and the aluminum alloyfilm is preferably an aluminum-silicon alloy film.

An uppermost Ti film is added to the barrier metal laminate including aTi film and a TiN film on the Ti film.

The semiconductor device according to the invention has a multilayeredelectrode structure including a three-layered barrier metal laminate,formed of a Ti film, a TiN film on the Ti film, and a Ti film on the TiNfilm, and an Al film or an Al—Si alloy film laminated on thethree-layered barrier metal laminate. Even if the undercoating barriermetal laminate is exposed as the Al film or the Al—Si alloy film is setback by side etching, the exposed barrier metal laminate will beprotected by the uppermost Ti film exhibiting excellent moistureresistance. Since the Ti atoms in the uppermost surface portion of thebarrier metal laminate react with the Si atoms in the aluminum alloyfilm, producing titanium silicides, the Si atoms in the Al—Si alloy filmdo not cause Si nodules. Therefore, Si nodules larger than 1 μm indiameter will not be caused by the heat treatment conducted at ahigh-temperature for a long time after the electrode wiring formation.Moreover, since any SiN film is not employed, the cracks that may becaused in the SiN film by the wire bonding conducted in the assemblyprocess are prevented from occurring. Therefore, the failures caused bythe cracks are reduced.

According to the invention, a semiconductor device including a metalelectrode wiring laminate and the method of manufacturing thesemiconductor device are obtained. The metal electrode wiring laminateaccording to the invention facilitates improving the moisture resistanceof the exposed portion of the barrier metal laminate thereof. The metalelectrode wiring laminate according to the invention facilitatespreventing the failures due to the cracks from causing even when thepassivation film is single-layered. The metal electrode wiring laminateaccording to the invention also facilitates preventing the failurescaused by the growth of the Si nodules remaining in the aluminum alloyfrom increasing.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to certain preferredembodiments thereof and the accompanying drawings, wherein:

FIGS. 1( a) through 1(d) are cross sectional views describing the steps(a) through (d) for manufacturing a metal electrode wiring laminate in asemiconductor device according to the invention;

FIGS. 2( e) through 2(h) are cross sectional views describing the steps(e) through (h) for manufacturing the metal electrode wiring laminate inthe semiconductor device according to the invention;

FIGS. 3( a) through 3(e) are cross sectional views describing the steps(a) through (e) for manufacturing a metal electrode wiring laminate in asemiconductor device according to the prior art;

FIGS. 4( f) through 4(i) are cross sectional views describing the steps(f) through (i) for manufacturing the metal electrode wiring laminate inthe semiconductor device according to the prior art;

FIG. 5 is a graph relating the thickness of an uppermost Ti film in athree-layered barrier metal laminate with the corrosiveness thereof; and

FIG. 6 is a graph relating the thickness of the uppermost Ti film in thethree-layered barrier metal laminate with the warp of a silicon wafer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now the process flow for manufacturing the semiconductor deviceaccording to a first embodiment that includes a metal electrode wiringlaminate including a barrier metal laminate, formed of a Ti film, a TiNfilm on the Ti film, a Ti film on the TiN film, and an Al—Si film on thebarrier metal laminate will be described below with reference to FIGS.1( a) through 1(d) and FIGS. 2( e) through 2(h). The semiconductordevice and the manufacturing method thereof according to the firstembodiment are the same with the conventional semiconductor device andthe conventional manufacturing method thereof in many aspects.Therefore, duplicated descriptions on the semiconductor device and themanufacturing method thereof according to the first embodiment will beavoided. In other words, the semiconductor device and the manufacturingmethod thereof according to the first embodiment will be describedmainly in connection with the differences thereof from the semiconductordevice that includes the conventional metal electrode wiring laminateand the conventional manufacturing method.

As shown in FIG. 1( a), a metal electrode wiring laminate including Tifilm 3, TiN film 4, Ti film 9, and Al—Si film 2 is formed by sputteringon a not-shown silicon substrate (step (a)). Ti film 3, TiN film 4, andTi film 9 are called collectively as a “barrier metal laminate”. An Alfilm may be used in substitution for Al—Si film 2. It is preferable forthe Al film or Al—Si film 2 to be 3 μm or more in thickness. Ti film 9,the third film on the silicon substrate side, is formed to be 20 nm to100 nm in thickness. The preferable thickness range for Ti film 9 willbe described below.

FIG. 5 describes the correlation between the thickness of Ti film 9 andthe period of time that elapses before a failure is caused by corrosion.In the corrosion resistance test, corrosions are caused in a very humidenvironment. Therefore, the period of time that elapses before a failureis caused by corrosion will be referred to hereinafter as the “moistureresistance time”. In FIG. 5, the horizontal axis represents thethickness of Ti film 9 and the vertical axis the moisture resistancetimes. When Ti film 9 is thinner than 20 nm, the moisture resistancetime is close to or shorter than the guarantee time as described in FIG.5. Therefore, sufficient moisture resistance can not be secured, when Tifilm 9 is thinner than 20 nm. When Ti film 9 is set to be more than 100nm in thickness, the moisture resistance tends to saturate. In otherwords, it is almost hard for Ti film 9, more than 100 nm in thickness,to further improve the moisture resistance thereof. Therefore, it ispreferable to set the thickness of Ti film 9 in the range between 20 nmand 100 nm. The environmental conditions for the corrosion test includesthe load conditions of 120° C. and 85 RH and the applied voltage of 80%of the rated Vice. The failure is defined by the increase of the reverseleakage current between the collector and the emitter that exceeds apredetermined value. The test time that elapses until the above-definedfailure is caused is described as the moisture resistance time in FIG.5.

As FIG. 6 indicates, the warps caused in the wafer in the Ti filmthickness range between 20 nm and 100 nm are from 1 mm to 2 mm, fallingalmost within the device limit of 2 mm. The wafer thickness in FIG. 6is, for example, 140 μm and the wafer diameter is, for example, 150 mm.When a wafer, the thickness thereof has been reduced to be 140 μm in thepreceding wafer process, is warping for 2 mm or more, the wafer may bebrought into contact with transportation equipments in the subsequentwafer process. The transportation equipments include a spin coater(coating equipment) for coating a polyimide film and a spin etcher. As aresult, the wafer may be broken by the contact. Therefore, the waferwarping for 2 mm or more can not be made to flow through the subsequentprocess. The limit, beyond which the troubles as described above will becaused, is referred to as the “device limit”.

The photoresist 1 is then coated on Al—Si film 2 and photoresist 1 ispatterned with a predetermined wiring pattern in the same manner asdescribed with reference to FIG. 3( b) (step (b)).

As described in FIG. 1( c), Al—Si alloy film 2, 3 μm or more inthickness, is etched by wet etching in the same manner as described withreference to FIG. 3( c) with a mixed acid (containing nitric acid,acetic acid, and phosphoric acid) using patterned photoresist 1 for amask (step (c)). Since the anisotropic etching caused by the wet etchingis small, Al—Si alloy film 2 is etched in the thickness directionthereof from the opening of photoresist 1. Al—Si alloy film 2 is etchedalso laterally (in the width direction) to the underside of photoresist1, resulting in side etching. After the etching of Al—Si alloy film 2 isover, Si nodules 5 remain on the surface of Ti film 9, the uppermostlayer of the exposed barrier metal laminate below Al—Si alloy film 2. Inthe same manner, Si nodules 5 are caused also in Al—Si alloy film 2.

As described in FIG. 1( d), Si nodules 5 remaining on the surface of Tifilm 9 are removed in the same manner as described with reference toFIG. 3( d) by plasma etching using a fluorine-containing gas as a mainetching gas (step (d)).

As described in FIG. 2( e), the three-layered barrier metal laminateincluding Ti film 3, TiN film 4 and Ti film 9 is etched and patterned inthe same manner as described with reference to FIG. 3( e) by dry etchingusing a chlorine-containing gas as a main etching gas and photoresist 1as a mask (step (e)). Since Al—Si alloy film 2 is etched off for acertain distance from the pattern edge of photoresist 1 by the sideetching described above, the barrier metal laminate is exposed partly.Since Ti film 9 is on the upper surface side of the barrier metallaminate, the moisture resistance of the barrier metal laminate issecured according to the first embodiment in contrast to theconventional barrier metal laminate. Since Ti film 9 is added to theupper surface side of the barrier metal laminate according to the firstembodiment, it is not necessary to add many more steps for securing themoisture resistance of the barrier metal laminate. Since Ti film 9 isformed subsequently to forming the TiN film, it is not necessary toprepare a new mask.

As described in FIG. 2 (f), the photoresist 1 is burned to ashes withoxygen plasma (step (f)).

As described in FIG. 2 (g), a heat treatment is conducted to sinter Tifilm 3, TiN film 4, Ti film 9 and Al—Si alloy film 2 (step (g)). Theheat treatment makes Si nodules 5 remaining in Al—Si alloy film 2 reactwith Ti film 9 below Al—Si alloy film 2, forming titanium silicide(Ti_(X)Si) 10. Therefore, Si nodules 5 are reduced in the number thereofas well as in the size thereof.

As described in FIG. 2 (h), polyimide film 7 is formed as a passivationfilm (protection film) (step (h)).

The semiconductor device according to the invention includes a metalelectrode wiring laminate including a three-layered barrier metallaminate, formed of Ti film 3, TiN film 4, and Ti film 9, and Al—Sialloy film 2. Since Ti film 9 is on the upper surface side of thebarrier metal laminate below Al—Si alloy film 2, the portion of thebarrier metal laminate, which will be exposed by the etching for formingthe electrode wiring, is covered with Ti film 9. Therefore, thecorrosion resistance (moisture resistance) of the portion of the barriermetal laminate, which will be exposed by the etching for forming theelectrode wiring, is improved by a small number of manufacturing steps.Since Si nodules 5 are prevented from causing in Al—Si alloy film 2according to the invention, cracks are prevented from causing in thewire bonding step.

While the present invention has been particularly shown and describedwith reference to the preferred embodiment thereof, it will beunderstood by those skilled in the art that the foregoing and otherchanges in form and details can be made without departing from thespirit and scope of the present invention. All modifications andequivalents attainable by one versed in the art from the presentdisclosure within the scope and spirit of the present invention are tobe included as further embodiments of the invention. The scope of thepresent invention accordingly is to be defined as set forth in theappended claims.

What is claimed is:
 1. A method of manufacturing a semiconductor device,the method comprising the steps of: forming a barrier metal laminate ona semiconductor substrate, the barrier metal laminate comprisingtitanium films and a titanium nitride film between the titanium films;forming an aluminum film or an aluminum alloy film on an uppermost oneof the titanium films in the barrier metal laminate; etching thealuminum film or the aluminum alloy film by wet etching using a mixedacid for patterning the aluminum film or the aluminum alloy film with apredetermined wiring pattern; etching a residue remaining on an exposedsurface portion of the barrier metal laminate by plasma etching using amixed gas comprising a fluorine-containing gas for removing the residue;etching the barrier metal laminate by plasma etching using a mixed gascomprising a chlorine-containing gas for patterning the barrier metallaminate with the predetermined wiring pattern; and coating an organicpassivation film.
 2. The method according to claim 1, wherein the mixedacid comprises nitric acid and acetic acid or the mixed acid comprisesnitric acid, acetic acid, and phosphoric acid.
 3. The method accordingto claim 1, wherein the uppermost one of the titanium films is from 20nm to 100 nm in thickness.
 4. The method according to claim 1, whereinthe aluminum film or the aluminum alloy film is 3 μm or more inthickness.
 5. The method according to claim 1, wherein the semiconductorsubstrate comprises a silicon semiconductor substrate and the aluminumalloy film comprises an aluminum-silicon alloy film.